Oh conh



naphthyl residue.

: ble general formula:

"Patented June 20, 1933 CAM. PAT. ounce:

miss S ES Elmo FONT M R- & COMPANY,

AWAR p p .A O 'nYns'rnsFs-Ann '1 N Drawin j ra'rsnr o FicE LD EDWARDWOCDWARD, OF PENN? GROVE, JERSEY,iASSIG-I TOR TO E. I. DU VTILEETNGTQN,EELAl/VAEE, A CORPORATION OF Application file d December 4, 193 Serialin. 579,104;

This invention relates to the production of and -H, and coupling theresultant product chemical compounds, and nore particularly to azo dyescontaining no sulphonic orcarboxylic groups.

The invention has as an object the produc tion of new chemicalcompounds, new disazo dyes valuable for coloring}; organic liquids andsolids, "particularly hydrocarbons and halogenated hydrocarbons, and ingeneral an advancement of the art. Other objects of the inventionwill beapparent by reference to the following description thereof,

These objectsareaccomplished by producing compounds having the'followingprobacon (alkyl) noun (alkyl),

m alkyl G aryl,

and QCONI wherein the two valence bonds of the nitrogen are part of aheterocyclic ns'a l v Zis a group which'anaybe H orNI-l n is 1 or 2 andmay be zero if R is :1

Compounds of. the type above described are obtained by diazotizing anaromatic amine of the benzene or naphtl'ia-lene series having; nocarboxylic or sulphonic groups and contaiininggas substituents one ormore mem hers-of the; group consisting of -alkyl -()-alkyl, -CH N nk ni,-O C ILN (alkyl) 2 naphthaleneseries capable of coupling in the witlanamino compound of the benzene or and -CON= \vherein the two valencebonds of the nitrogen are part of a heterocyclic While the invention issusceptible of considerable variation and modification in the manner of,itspractical application, particularly as regards the Various productsobt ained and conditions oftelnperature, proportions ofmaterial, etcl,involved in their preparation, the -foll0wing examples will illustratesome of the products fallingwithin the invention and how they may beprepared. The proportions are given in parts by Weight.

Example The amino-azohydrochloride prepared fro1n123 parts of para-anishdine diazotized and coupled with 143 parts of alpha-naphthylaminelisstirred with 6000 parts of water and diazotized with parts ofhydrochloric acid (100%) and 7 6 parts of sodium nitrite for one hour at10 The brown diazo solution is filtered and run into a solution of 152parts of beta-naphthol, 44 parts of sodium hydroxide and 106 parts ofsodium carbonate in 2000 parts ofwater at 5 C. When the coupling iscompleteuthe color is filtered at (I, washed with Wator and dried at 60C. The product is a black powder insoluble in water, but soluble inacetone, chloroform, carbon tetrachloride, ethylene dichloride, ethylenedibromidmgasoline, kerosene, benzene, toluene, chloroben zene,nitrobenzene, and alphwchloro-naphisms is thalene with a bluish-redcolor. The maxi} Ewamplc 2.The amino-axo-hydrocliloride prepared from137 parts of para-phenee tidine diazotized and coupledwith'173 parts of1-amino-2-naphthol-methyLether is stirred with 6000 parts of water anddiazotized with parts of hydrochloric acid (100%) and 76 parts of sodiumnitrite for one hour at 10 C. The brown diazo solution is filtered andrun into a solu'tionof 152 parts of betanaphthol, 44 parts of sodiumhydroxide and 100 partsof sodium carbonate in 2000 parts of water at 5C. When the couplingis complete the insoluble color is filtered off at(1., washed and dried. The product is a black powder, soluble in benzol,gasoline and many other organic liquids with a blue-violet color. Themaximum absorption of light in its gasoline solution is at about 580millimicrons.

Its constitution may be represented by the following formula:

Example 3.The amino-azo-hydrochloride prepared from 153 parts ofamino-hydroquinone-dimethyl-ether,. diazotized and coupled with 173parts of 1-amino-2-napholine and other organic liquids, with a bluecolor. The maximum absorption of light in its gasoline solution is atabout 595 millimicrons.

The following formula represents its constitution v 3cm 1cm m(|JO.NH.C2H5

OCH: 7

i like.

55 parts of hydrochloric acid (100%). It is then diazotized with 76parts of sodium nitrite at 10 C. for two hours. The insoluble diazocompound is added to a solution of 227 parts of2-hydroxy-3-ethyl-naphthamide and 80 parts of sodium hydroxide in 800parts of alcohol and 1000 parts of water at 510 C. After the coupling iscomplete the color is filtered off at 50 C. washed and dried. Theproduct is a blacl: powder soluble in benzene and other organic solventswith a green color. The maximum absorption of light in its gasolinesolution is at about 60 millimicrons. V

Its constitution may be represented by the following structural formula:

OOH; (RH G'ONH. C211 It will be understood that the above examples arenot intended to limit the scope of the invention. As previouslyindicated the methods of preparation may be varied widely,particularly-as regards such details as the proportions of the reactingsubstances and conditions of temperature, volumes, and the acterdescribed in the general formula, and different combinations of thoseused in the examples may be employed.

First components which are preferably employed are para-anisidine.para-phenetidine, amino-hydroquinone-dimethyl-ether,alpha-naphthylamine, t-amino-pyrocatecholdimethyl-ether, symmetricalamino-pyrogallol-trimethyl-ether, para-amino-benzyl- .dimethyl-aniline,omega dimethyl a1ninopara-phenetidine, and beta-naphthylamine.

Second components which give especially desirable results arealpha-naphthylamine, 1-,

amino-2-naphthol-methyl-ether, amino-hydroquinone-ether, naphthol. r r 7As last component-s, beta-naphthol, 1- amino-7-naphthol,2-hydroxy-3-naphthoyl piperidide, 2-hydroxy-3-naphth0yl cyclohexylamide,alkyl and alkyl-aryl derivatives of 2-hydroxy-3-naphthamideare-preferred.

For purposes of interpretation,the nomenclature used in thespecification and claims may be defined as follows. An alkyl group is anacyclic radical derived from a hydrocarbon by the elimination of oneatom of hydrogen. An alkoxy radical, which is also written O-alkyl, isan acyclic oxy-alkyl radical such as, for example, -OCH *OC H and thelike. An aryl group is an cresidine, and 1-am1no-7- Anyotherintermediate of the chariso-cyclic radical of the-benzene,diphenyl, or

I naphthalene series which may or may not be 7 able formula saturated.

Compounds of the type herein described are especially well adapted tocoloring organic liquids and solids, particularly gaso-- line and otherhydrocarbons and halogenated hydrocarbons. In general, about 5-20milligrams of dye per liter of organic liquid gives a pleasing depth ofcolor.

As many apparent and widely di'flerent embodiments of this invention maybe made without departing from the spirit and scope thereof, it is to beunderstood that I do not limit myself to the specific embodimentsthereof except as defined by the appended claims; I p

I claim:

1. A chemical compound having the prob and may be -H if R is a naphthylresidue, Y

is a member of the group consisting of -I-I, -CON (alkyl) -CONH(alkyl),

and -C()N= wherein the two valence bonds of the nltrogen are part of aheterocyclic rmg,

Z is a group which may be -H or -NH and n islor 2 and may be zero if Ris a naphthyl residue. I

2. The chemical compound set forth in claim 1 wherein R is an. aromaticradical of the benzene series containing no sulphonic or carboxylicgroups. a

3. The chemical compound set forth in claim 1 wherein X is one or morealkoxy groups. l

4. The chemical compound set forth in claim 1 wherein R is a naphthalenederivative with the azo groups para to each other and containing nosulphonic or carboxylic groups.

an aromatic radical of the benzene series containing no sulphonic orcarboxylic groups, R is a naphthalene radical with the azo groups parato each other and containing no sulphonic or carboXylic groups, X is oneor 7. The process of preparing an azo dye.. compound which comprisesdiazotizlng alpha-naphthylamine, coupling the resultant product withl-amino-2-naphthol-msthylether, diazotizing the resultant amino-azocompoundv and coupling with 2-hydroXy3-- ethyl-naphthamide.

8. The process of preparlng an azo dye compound which comprisesdiazotlzlng an aromatic amine of the benzene or naphthalene serleshaving no carboxylic or sulphonic groups and containing as substituentsone or more members of the group consisting of -alkyl, -O-alkyl, CHN(-alkyl)- -OG H N(alkyl) and -H, coupling the resultant prod net withan amino compound of the benzene or naphthalene series capable ofcoupling para to the amino group, containing as a sub-' ing. of -H,-CON(alkyl) -CONH(alkyl) alkyl and CON= wherein the two valence bondsthe resultant amino-azo compound and coupling it with beta-naphthol. I

10. The process of preparing an azo dye which comprises diazotizingamino-hydroquinone-dimethyl-ether, coupling the resultant product withmethyl-ether, diazotizing the resultant amino-azo compound and couplingit with 2-hydroxy-3-ethyl-naphthamide.

11. An azo dye having the following probable formula:

1-amino-2-naphtholmore methoiry radicals, Yis a member of the 12. An azodye having the folowing probable formula: 7

00m, 0H CONIELCzHs gm gm-v In testimony whereof I aflix my signature.

HAROLD E. WOODWARD.

